Reaction kinetics of the solid state polymerization of poly(bisphenol A carbonate)

Chunmei Shi, Stephen Gross, Joseph M. DeSimone, Douglas J. Kiserow, George W. Roberts

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The kinetics of solid-state polymerization (SSP) of poly(bisphenol A carbonate) was investigated with N2 as the sweep gas. The N2 flow rate and prepolymer particle size were chosen to eliminate the influence of both external and internal phenol diffusion, and to ensure that the kinetics was controlled by the rate of the forward transesterification reaction. The forward reaction rate constants were evaluated at different temperatures between 120 and 165 °C, and the activation energy for SSP of poly(bisphenol A carbonate) with N2 as the sweep gas was determined to be 99.6 kJ/mol. At each temperature, the polymer molecular weight increased with time, eventually reaching an asymptotic value. The asymptotic molecular weight increased with temperature. The glass transition temperature (Tg) of the polymer increased as the molecular weight increased. At lower reaction temperatures, Tg approaches the reaction temperature as the polymerization proceeds, and the achievable molecular weight appears to be limited by decreased end group mobility. At the highest reaction temperature, which was well above the final Tg of the polymer, the stoichiometric ratio of the two end groups appears to determine the achievable molecular weight.

Original languageEnglish
Pages (from-to)2060-2064
Number of pages5
JournalMacromolecules
Volume34
Issue number7
DOIs
StatePublished - Mar 27 2001
Externally publishedYes

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Carbonates
Reaction kinetics
Polymerization
Molecular weight
Polymers
Temperature
Gases
Kinetics
Transesterification
Phenol
Phenols
Reaction rates
bisphenol A
Rate constants
Activation energy
Particle size
Flow rate

All Science Journal Classification (ASJC) codes

  • Materials Chemistry

Cite this

Reaction kinetics of the solid state polymerization of poly(bisphenol A carbonate). / Shi, Chunmei; Gross, Stephen; DeSimone, Joseph M.; Kiserow, Douglas J.; Roberts, George W.

In: Macromolecules, Vol. 34, No. 7, 27.03.2001, p. 2060-2064.

Research output: Contribution to journalArticle

Shi, Chunmei ; Gross, Stephen ; DeSimone, Joseph M. ; Kiserow, Douglas J. ; Roberts, George W. / Reaction kinetics of the solid state polymerization of poly(bisphenol A carbonate). In: Macromolecules. 2001 ; Vol. 34, No. 7. pp. 2060-2064.
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AU - Roberts, George W.

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AB - The kinetics of solid-state polymerization (SSP) of poly(bisphenol A carbonate) was investigated with N2 as the sweep gas. The N2 flow rate and prepolymer particle size were chosen to eliminate the influence of both external and internal phenol diffusion, and to ensure that the kinetics was controlled by the rate of the forward transesterification reaction. The forward reaction rate constants were evaluated at different temperatures between 120 and 165 °C, and the activation energy for SSP of poly(bisphenol A carbonate) with N2 as the sweep gas was determined to be 99.6 kJ/mol. At each temperature, the polymer molecular weight increased with time, eventually reaching an asymptotic value. The asymptotic molecular weight increased with temperature. The glass transition temperature (Tg) of the polymer increased as the molecular weight increased. At lower reaction temperatures, Tg approaches the reaction temperature as the polymerization proceeds, and the achievable molecular weight appears to be limited by decreased end group mobility. At the highest reaction temperature, which was well above the final Tg of the polymer, the stoichiometric ratio of the two end groups appears to determine the achievable molecular weight.

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